Glycosyl Exchange of Unactivated Glycosidic Bonds: Suppressing or Embracing Side Reactivity in Catalytic Glycosylations.

While developing boron-catalyzed glycosylations using glycosyl fluoride donors and trialkylsilyl ether acceptors, competing pathways involving productive glycosylation or glycosyl exchange were observed. Experimental and computational mechanistic studies suggest a novel mode of reactivity where a dioxolenium ion is a key intermediate that promotes both pathways through addition to either a silyl ether or to the acetal of an existing glycosidic linkage. Modifications in catalyst structure enable either pathway to be favored, and with this understanding, improved multicomponent iterative couplings and glycosyl exchange processes were demonstrated.

Narratives of Undergraduate Research, Mentorship, and Teaching at UCLA.

This work describes select narratives pertaining to undergraduate teaching and mentorship at UCLA Chemistry and Biochemistry by Alex Spokoyny and his junior colleagues. Specifically, we discuss how individual undergraduate researchers contributed and jump-started multiple research themes since the conception of our research laboratory. This work also describes several recent innovations in the inorganic and general chemistry courses taught by Spokoyny at UCLA with a focus of nurturing appreciation for research and creative process in sciences including the use of social media platforms.

Fluoride Migration Catalysis Enables Simple, Stereoselective, and Iterative Glycosylation.

Challenges in the assembly of glycosidic bonds in oligosaccharides and glycoconjugates pose a bottleneck in enabling the remarkable promise of advances in the glycosciences. Here, we report a strategy that applies unique features of highly electrophilic boron catalysts, such as tris(pentafluorophenyl)borane, in addressing a number of the current limitations of methods in glycoside synthesis. This approach utilizes glycosyl fluoride donors and silyl ether acceptors while tolerating the Lewis basic environment found in carbohydrates. The method can be carried out at room temperature using air- and moisture-stable forms of the catalyst, with loadings as low as 0.5 mol %. These characteristics enable a wide array of glycosylation patterns to be accessed, including all C1-C2 stereochemical relationships in the glucose, mannose, and rhamnose series. This method allows one-pot, iterative glycosylations to generate oligosaccharides directly from monosaccharide building blocks. These advances enable the rapid and experimentally straightforward preparation of complex oligosaccharide units from simple building blocks.

Oxidative Generation of Boron-Centered Radicals in Carboranes.

We report the first indirect observation and use of boron vertex-centered carboranyl radicals generated by the oxidation of modified carboranyl precursors. These radical intermediates are formed by the direct oxidation of a B-B bond between a boron cluster cage and an exopolyhedral boron-based substituent (e.g., -BF3K, -B(OH)2). The in situ generated radical species are shown to be competent substrates in reactions with oxygen-based radicals, dichalcogenides, and N-heterocycles, yielding the corresponding substituted carboranes containing B-O, B-S, B-Se, B-Te, and B-C bonds. Remarkably, this chemistry tolerates various electronic environments, providing access to facile substitution chemistry at both electron-rich and electron-poor B-H vertices in carboranes.

Cage-Walking: Vertex Differentiation by Palladium-Catalyzed Isomerization of B(9)-Bromo-meta-Carborane.

We report the first observed Pd-catalyzed isomerization ("cage-walking") of B(9)-bromo-meta-carborane during Pd-catalyzed cross-coupling, which enables the formation of B-O and B-N bonds at all boron vertices (B(2), B(4), B(5), and B(9)) of meta-carborane. Experimental and theoretical studies suggest this isomerization mechanism is strongly influenced by the steric crowding at the Pd catalyst by either a biaryl phosphine ligand and/or substrate. Ultimately, this "cage-walking" process provides a unique pathway to preferentially introduce functional groups at the B(2) vertex using B(9)-bromo-meta-carborane as the sole starting material through substrate control.

B-N, B-O, and B-CN Bond Formation via Palladium-Catalyzed Cross-Coupling of B-Bromo-Carboranes.

Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, and -CN) and multiple functional groups onto the boron-rich clusters.